EA022128B1 - Solid herbicide compositions with built-in adjuvant - Google Patents

Abstract

The present invention concerns stable herbicidal solid compositions containing built-in adjuvant which exhibit improved herbicidal efficacy when used to control weeds in flooded rice paddies or fields.

Description

This invention relates to stable solid compositions, such as granules and powders containing herbicides and an integral adjuvant, and methods for their preparation and use. Such solid compositions exhibit an improved herbicidal effect on weeds in applications for flooded rice fields.

Agrochemical compositions are generally developed based on customer needs and the physicochemical properties of the active ingredients, for example, the solubility of the active ingredient in water or in anhydrous solvents. There are two main categories of compositions, solid compositions and liquid compositions.

Granular products containing agricultural active ingredients constitute one class of solid compositions that are in increasing demand today because of their relative safety compared to liquid compositions and the advantages they provide in terms of reducing packaging and transportation costs. Granular products in the form of emulsifiable granules (EG), water-dispersible granules (DG) and granules (GR) for use by spreading can be useful for controlling insects, weeds, fungal pathogens and nematodes and are often used in soils and aquatic environments . Due to the substantial weight of the particles, the granules used in airborne applications can present a reduced risk of inappropriate drift compared to liquid spraying in the air.

Products in the form of a powder or wettable powder (SP) containing active agricultural ingredients are additional classes of solid compositions that are also used in agriculture and which differ from granules, primarily due to their smaller particle size. Granules typically have a size range between 200 and 4000 microns (Wikipedia: Granulation - producing granules) and they are much larger than particles in powder compositions and therefore pose less risk of inhalation. Granular products can be obtained from powders or wettable powders by agglomeration or granulation.

The active ingredients in the form of solid particles or liquids may be formulated into granules and may include insecticides, herbicides, fungicides, nematicides and plant growth regulators. Granular compositions typically contain a relatively small amount of active ingredient, since granules are often not further diluted with a carrier solution, such as water, before use, but are instead applied directly to a region of interest, such as, for example, soil or water.

After application, the active ingredient contained in the granule is released into the field of application, usually in contact with water.

Agricultural granules containing the active ingredients also contain solid inert ingredients that can serve as a diluent and / or help maintain the granules in a solid state. These solid inert ingredients may include, for example, clays, starches, silicas, sulfates, chlorides, lignosulfonates, carbohydrates such as dextrins, alkyl cellulose, xanthan gum and guar gum, and synthetic polymers such as polyvinyl alcohols, sodium polyacrylates, polyethylene oxides polyvinylpyrrolidones and urea / polyformaldehydes, such as RegdoRac M® (registered trademark A1beshag1e Sogrogayoi). The active ingredient (s) contained in the granule can be melted into a liquid, dissolved in a solvent or dispersed in a liquid, which can then be sprayed on or absorbed by solid inert ingredients. In the absence of effective solid inert ingredients, dry granules can be physically unstable and, in the case of solid particles, slowly disintegrate to form dust or powder, or in the case of granules containing inherent liquid adjuvants, slowly disintegrate, forming large liquid droplets as a result of Ostwald ripening. Many solid inert ingredients used in agricultural granular formulations generally have good water solubility or dispersibility.

Excipients are important components of granules and are defined as substances that can increase the biological activity of the active ingredient, but they themselves have negligible biological activity.

Auxiliary agents improve the effectiveness of the active ingredient, for example, by improving the delivery and uptake of the herbicide by the target weed, providing a more effective biological control.

Aids in the form of solid particles or liquids can be added directly to the formulated agricultural product, such as a pellet, to provide greater product efficiency in its application. Typically, adjuvants used may include, for example, surfactants, dispersants, oil and vegetable oils, solvents, and wetting agents. Examples of commonly used adjuvants include, but are not limited to, paraffin oil, fruit spray oils (e.g. summer oil), methyl rapeseed oil, methylated soybean oil, highly refined vegetable oil and the like, fatty acid esters of polyhydric alcohol 1 022128 ta, polyethoxylated esters, ethoxylated alcohols, alkyl polysaccharides and mixtures, aminethoxylates, ethoxylates of fatty acid ester and sorbitan, polyethylene glycol esters, organosilicon e surfactants, ethylene vinyl acetate terpolymers, ethoxylated esters alkilarilfosfatnye etc. These and other auxiliaries are described in the publication Sotreysht o Н с е Ы И Ай Ай щ щ Η Η Η η η η, ed. Vguap Woapd, Department of Plant, Soil, and Agricultural Systems, University of Southern Illinois MS-4415, 1205 Lincoln Drive, Carbondale, Illinois 62 901, which is available for viewing on the Internet at 1Br: // \ y \ y \ y.11egY ^ e -a4shchuap15 .sot./

The term integral adjuvant refers to one or more adjuvants added to a particular composition, such as a granular or liquid composition, at the stage of preparation of the product, and not prior to use of the product, such as, for example, a spray solution. The use of integral aids simplifies the use of agrochemical products for the end user by reducing the number of ingredients that need to be individually measured and applied.

Rice is an important cereal cultivated in many parts of the world, and it is grown in both wet and dry conditions. Rice weed control is critical to maintaining high levels of agricultural productivity. The use of herbicidal granules for weed control in flooded rice fields and fields is a very common agronomic practice in many rice growing regions. New granular herbicidal products are needed that provide greater efficacy compared to existing products.

Cygalofop-butyl, butyl ester of (2K) -2- [4- (4-cyano-2 fluorophenoxy) phenoxy] propionic acid (CA8 # 122008-78-0), is a member of the class of aryloxyphenoxypropionic acid herbicides known in the art as fop herbicides, and is used to control grassy weeds in rice. The cygalophop-butyl herbicide, known under the trade name Sypsil® (a registered trademark of Eo \ yAgto8s1epse8LTS). It is sold in granules (GR), compositions in the form of oil-in-water (ΕΑ) and emulsifiable concentrates (EC) and exhibits good selectivity for rice when used both on dry fields and on flooded checks.

Existing commercial granular cygalofop-butyl compositions contain a relatively large amount of solid inert ingredients, such as potassium chloride, clay or starch, combined with relatively small amounts of inherent adjuvants, such as aromatic solvents. In the products currently sold, these integral auxiliaries comprise a maximum of 15-20 wt.% Of the total weight of the granule with butylcygalophop. The limited content of an integral adjuvant in the pellets currently sold may limit the biological effectiveness of the cyhalophop-butyl herbicide due to the minimal action of the herbicidal adjuvant.

The present invention provides an improvement in existing solid herbicidal compositions used to control weed plants in rice by providing a higher content of an integral adjuvant, and thus suggests greater herbicidal efficacy against weeds in flooded rice fields or fields.

The present invention relates to a stable herbicidal granule containing an integral adjuvant, which includes:

a) a herbicide selected from the class of acetyl-CoA carboxylase or ALS enzyme inhibitors, comprising from 1 to 200 g / kg relative to the total weight of the composition;

b) an integral adjuvant comprising, in relation to the total weight of the composition, from 50 to 750 g / kg;

c) a solid carbohydrate comprising, in relation to the total weight of the composition, from 10 to 700 g / kg;

ά) a solid water-soluble polymer or oligomer, comprising, in relation to the total weight of the composition, from 50 to 700 g / kg, provided that the solid carbohydrate and the solid water-soluble polymer or oligomer should together be at least 200 g / kg total composition.

The present invention also relates to a stable herbicidal powder containing an integral adjuvant.

Another aspect of the present invention relates to a stable solid herbicidal composition containing an integral adjuvant, which includes:

a) a herbicide selected from compounds of the formula

where Ar is a phenyl group substituted with one to four substituents independently selected from halogen, C ^ -Cb alkyl, C ^ -Cb alkoxy, C ₂ -C ₄ alkoxyalkyl, C ₂ -C ₆ alkylcarbonyl, C ₁ -C _b alkylthio groups, C ₁ -C _b halogenated, C ₁ -C _b halogenated, C ₂ -C ₄ halogenated, C ₂ -C _b halogenated, C ₁ -C _b halogenated, -OCH ₂ CH ₂ -, - OCH ₂ CH ₂ CH ₂ -, -OCH ₂ O- or -OCH ₂ CH ₂ O-;

K represents H or P;

X is C1 or vinyl;

Υ represents C1, vinyl or methoxy group, their salts and esters;

component in relation to the total weight of the composition from 1 to 200 g / kg;

b) an integral adjuvant comprising, in relation to the total weight of the composition, from 50 to 750 g / kg;

c) a solid carbohydrate comprising, in relation to the total weight of the composition, from 10 to 700 g / kg;

b) a solid water-soluble polymer or oligomer, comprising, in relation to the total weight of the composition, from 50 to 700 g / kg, provided that the solid carbohydrate and the solid water-soluble polymer or oligomer must together be at least 200 g / kg of total composition.

Another aspect of the present invention relates to a method for controlling undesirable vegetation in an aqueous medium using solid herbicidal compositions or spray solutions obtained from solid herbicidal compositions for agricultural purposes, such as improving weed control in flooded rice fields and fields.

Another aspect of the present invention relates to a method for producing a solid herbicidal composition, which may be granules or powder.

Agricultural active ingredients that have low water solubility are sometimes difficult to apply effectively to crops to kill pests. This situation is especially critical when the active ingredients are not applied directly to the foliage of the plant, for example, when granular herbicidal products are used to control weeds in flooded rice fields. The herbicidal granules used in flooded rice receipts are typically added directly to the rice rice water and they have very little direct contact with the foliage of the plant during application. For example, cygalofop-butyl is a herbicidal active ingredient which, when added to the water in the form of granules, requires the presence of an integral adjuvant to ensure the necessary delivery and absorption of the herbicide by the target weed and to achieve acceptable levels of weed control.

Pellets, which may have a higher content of essential aids based on the number of grams of active ingredient per hectare (gai / ha), can provide more effective weed control in aquatic environments such as flooded rice fields.

The solid compositions of the present invention are those solid agricultural compositions that contain active ingredients and inert ingredients and which include granules, dispersible granules, emulsifiable granules, powders, wettable powders and the like.

Resistant solid compositions are generally defined as those that are physically and chemically resistant to the environment in which they are received and stored. Sustainability includes inhibiting the leakage or loss of ingredients contained in a solid composition, especially liquid ingredients, such as a liquid active ingredient or an integral liquid adjuvant.

The solid composition of the present invention can have a high content of an integral adjuvant by combining the solid carbohydrate with one or more solid water-soluble polymers or oligomers that together stabilize the solid composition during its preparation and storage.

The solid composition of the present invention consists of an active herbicidal ingredient, an essential adjuvant, a solid carbohydrate and a solid water-soluble polymer or oligomer.

The herbicidally active ingredient of the present invention can be selected from the herbicides of the class of inhibitors of the enzyme acetyl-CoA carboxylase (acetyl coenzyme A carboxylase) or the herbicides of the class of inhibitor of the enzyme ALS (acetolactate synthase). Herbicidally active acetyl CoA carboxylase inhibiting ingredients known in the art as fop and dim herbicides include, but are not limited to, cygalofop-butyl, phenoxaprop-ethyl, fluazifop-R-butyl, haloxifopmethyl, haloxifop-K-methyl, metamifop , propaquizaphop, quisalofop-P-ethyl, quisalofop-P-tefuril and profoxydim.

Herbicidally active ALS inhibitory ingredients include, but are not limited to, azimsulfuron, bensulfuron-methyl, cloransulam-methyl, cyclosulfamuron, diclosulam, ethoxysulfuron, flurasulam, flucetosulfuron, flumetsulam, halosulfuron-methyl, metosulfuram, metosulfuram, metazosurfam methyl, propyrisulfuron, pyrazosulfuron-ethyl, pyroxulam, imazetapyr, imazamox, imazosulfuron and their derivatives. Herbicide active ingredient according to

- 3 022128 of the present invention generally has a water solubility of less than 3000 ppm, preferably less than 1000 ppm, and most preferably less than 100 ppm under ambient pH conditions (pH 6.5 to 7.5). With respect to the total weight of the composition, the herbicidal active ingredient is from 1 to 200 g / kg, preferably from 2 to 75 g / kg.

Additional herbicidally active ingredients of the present invention include compounds having the formula

where Ar is a phenyl group substituted with one to four substituents independently selected from halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₂ -C ₄ alkoxyalkyl, C ₂ -C ₆ alkylcarbonyl, C ₁ - C ₆ alkylthio groups, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ haloalkoxy groups, C ₂ -C ₄ haloalkoxyalkyl, C ₂ -C ₆ haloalkylcarbonyl, C ₁ -C ₆ haloalkylthio groups, -OCH ₂ CH ₂ -, -OCH ₂ CH ₂ CH ₂ -, —OCH ₂ O— or —OCH ₂ CH ₂ O—;

K represents H or P;

X is C1 or vinyl;

Υ represents C1, vinyl or a methoxy group, and their salts and esters, as disclosed, for example, in I87314849 B2, I87300907 B2, I87786044 B2 and I87642220 B2. A particularly suitable herbicide of this class is the compound

and its C ₁ -Sb alkyl esters or salt derivatives thereof, such as, for example, methyl ester, which in the present description is called compound A.

The integral adjuvant of the present invention may be liquid or solid and may include one or more non-ionic surfactants or a water-immiscible liquid. Nonionic surfactants that can be used as integral adjuvants of the present invention include, but are not limited to, fatty acid esters of polyhydric alcohol, polyethoxylated esters, polyethoxylated alcohols, alkyl derivatives of polysaccharides such as alkyl polyglycosides and their mixtures, amine ethoxylates, fatty acid and sorbitan ester ethoxylates, organosilicon surfactants, ethylene terpolymers and vinyl acetate a, ethoxylated alkylaryl phosphate esters and sucrose fatty acid esters.

Non-miscible liquids that can be used as integral adjuvants generally have a solubility in water of less than 1 vol% and may include, but are not limited to, petroleum distillates or hydrocarbons such as mineral oil, kerosene, paraffin oils mixed naphthalene and alkylnaphthalene fractions, aromatic solvents, in particular alkyl substituted benzenes, such as xylene or propylbenzene fractions, and the like; vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and etc .; esters of the above vegetable oils, such as 2-ethylhexyl stearate, n-butyl oleate, isopropyl myristate, propylene glycol dioleate and the like; and dibasic acid esters such as dioctyl succinate, dibutyl adipate, dioctyl phthalate, ditridecyl phthalate and the like.

Preferred integral adjuvants include one or more petroleum distillates or hydrocarbons such as mineral oil, paraffin oils and aromatic solvents such as xylene, propylbenzene fractions, alkylnaphthalene fractions, and the like; vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and etc .; C1-C6 esters of vegetable oils, such as methylated vegetable oils from seeds; dibasic acid esters such as dioctyl succinate, dibutyl adipate, dioctyl phthalate, ditridecyl phthalate and the like; fatty acid esters of polyhydric alcohol, polyethoxylated esters, polyethoxylated alcohols, alkyl derivatives of polysaccharides such as alkyl polyglycosides and mixtures thereof, amine ethoxylates, fatty acid ester ethoxylates, sorbitan esters, organosilicon surfactants, ethylene and vinyl acetate terpolymers

- 4 022128 ethoxylated alkylaryl phosphate esters and sucrose fatty acid esters.

The integral adjuvant of the present invention, with respect to the total weight of the composition, is from 50 to 750 g / kg, preferably from 200 to 600 g / kg and most preferably from 300 to 600 g / kg.

The solid carbohydrates of the present invention include monosaccharides, disaccharides or polysaccharides, and mixtures thereof having good water solubility or dispersibility. Solid carbohydrates include, for example, glucose, fructose, sucrose, trehalose, lactose and maltose, dextrins, starches, modified starches, modified celluloses, such as, for example, alkylated and carboxyalkylated celluloses, natural resins, such as, for example, guar gums, xanthan resins and guar gums from seeds, etc. and mixtures thereof. Preferred solid carbohydrates of the present invention are mono- and disaccharides.

The solid carbohydrate of the present invention may comprise, with respect to the total weight of the composition, from 10 to 700 g / kg, preferably from 10 to 500 g / kg and most preferably from 10 to 400 g / kg.

The solid water-soluble polymer or oligomer of the present invention includes one or more synthetic or partially synthetic polymers or oligomers that swell, disperse or dissolve in water at ambient temperature. Typical solid water-soluble polymers or oligomers include lignosulfonates, condensates of alkylnaphthalene sulfonate and formaldehyde, polyvinyl alcohols, polyacrylates, polyethylene oxides, polyvinylpyrrolidones and copolymers, their derivatives and mixtures.

Preferred solid water-soluble polymers or oligomers of the present invention include polyvinyl alcohols obtained by hydrolysis of polyvinyl acetate, which differ in the degree of hydrolysis from 87 to 99%, of which Ce1uo1® 205 (registered trademark 8ek1ksh Seshka1 Co., L4.), Lignosulfonates of which Woggekregke® ΝΑ (registered trademark of Voggedaog 4 PioTesk) is an example and condensates of alkylnaphthalene sulfonate and formaldehyde, of which Mogue1® Ό425 (registered constant prices trademark Ak / o №e1), and copolymers, derivatives and mixtures thereof.

The solid water-soluble polymer or oligomer of the present invention is in relation to the total weight of the composition from 50 to 700 g / kg, preferably from 100 to 600 g / kg and most preferably from 150 to 600 g / kg, provided that the solid carbohydrate and the solid water-soluble polymer or oligomer should together comprise at least 200 g / kg of the final composition.

In a typical method for preparing a solid composition of the present invention, the aqueous phase is obtained by mixing in water soluble in water or water dispersible ingredients, including, but not limited to, a solid water-soluble polymer or oligomer, a solid carbohydrate, and optionally any insoluble in oil active ingredient and other inert ingredients. The oil phase is obtained by mixing together any oil-soluble ingredients, including, but not limited to, inherent auxiliaries and oil-soluble active ingredients. The oil phase is slowly added to the aqueous phase during homogenization with a high shear rate until the desired mixture is obtained. Then the mixture is dried to obtain solid compositions directly in the form of granules or dried to obtain the powder of the present invention, which, optionally, can be further processed to obtain the granules of the present invention.

An example of a stable solid herbicidal composition of the present invention containing an integral adjuvant includes:

a) an active herbicidal ingredient comprising, relative to the total amount of the composition, from 2 to 75 g / kg of cygalofop-butyl;

b) an integral adjuvant comprising, with respect to the total weight of the composition, from 300 to 600 g / kg methyl soyate;

c) a solid carbohydrate comprising, in relation to the total weight of the composition, from 10 to 400 g / kg of sucrose;

4) a solid water-soluble polymer or oligomer, comprising, in relation to the total weight of the composition, from 10 to 100 g / kg of 86-89% hydrolyzed polyvinyl alcohol;

e) a solid water-soluble polymer or oligomer comprising, with respect to the total weight of the composition, from 150 to 600 g / kg of sodium lignosulfonate;

ί) optionally, other inert ingredients to be formulated.

Another aspect of the present invention relates to a method for controlling weeds by spreading or adding a solid herbicidal composition or spraying an aqueous solution or mixture obtained from a solid herbicidal composition in an aqueous medium, such as rice fields, ponds, lakes and watercourses and the like, to combat unwanted vegetation. In this aspect, a herbicidally effective amount of a solid herbicidal composition, or an aqueous spray solution, or mixtures obtained from a solid herbicidal composition, is applied to a water region to carry out an appropriate control of undesired weeds. The solid herbicidal composition or spray solutions obtained from the solid herbicidal composition are particularly useful for controlling grassy, broadleaf and sedge weeds in flooded rice fields or fields.

An additional aspect of the present invention relates to a method for producing solid herbicidal compositions.

Granular compositions can be obtained using one or more of the following processing methods: (1) disk granulation, (2) agglomeration by mixing, (3) extrusion granulation, (4) granulation in a fluidized bed, (5) granulation or agglomeration with spray and (6) drum granulation. In addition, granules can be prepared using a tablet press. It is important to consider the physicochemical properties of the active ingredient and additives when choosing the method used. O.A. Be11 and Ό.Α. Knojek in the publication SNMMU; · ιπά Tébnogo o £ AdgosNepps1 Rogtsiayop5, ed. Ό. A. KpoMek (K1k ^ ek Ac; Leins Riebkegk, 1998), p. 41-114 describe the types of granules used in agricultural chemical compositions, and provide many references to the preparation of these solid compositions. Powder compositions can be obtained by vacuum drying, rotary drying, spray drying, drum drying, or other processing methods known to those skilled in the art. In any of the processing methods described herein, additional inert ingredients may be added to the composition before, during or after processing to facilitate processing or improve the final quality or stability of the granules or powder. These additional inert ingredients may include, but are not limited to, flow improvers and caking agents, such as, for example, precipitated hydrophilic silica, hydrophilic fused silica and clays, anti-foaming agents, wetting agents, dispersing binders, dispersing agents. agents, solid diluents and carriers.

There are many examples where solid additives are used to stabilize water-insoluble liquids during processing to produce stable powders. Examples of such additives are gelatin, glycine, casein, water-soluble polymers such as polyvinyl alcohol, polyvinylpyrrolidone and polysaccharides. Some of these applications are described, for example, in US publications 4244836 and AO 2006/076943. However, they contain very limited attempts to stabilize essential aids during processing to produce agricultural granules or powders.

A method of obtaining stable solid herbicidal compositions of the present invention, which may have a high content of an integral auxiliary agent, includes:

(1) mixing all solid water-soluble polymers or oligomers and solid carbohydrate ingredients in water to form an aqueous phase;

(2) mixing an inherent adjuvant and oil soluble or oil dispersible active ingredients to form an oil phase;

(3) adding the oil phase obtained in stage (2) to the aqueous phase obtained in stage (1) during homogenization with a high shear rate to obtain a mixture;

(4) drying the mixture obtained in step (3) to obtain the stable granules or powder of the present invention.

The most optimal way to practice the above method to obtain stable solid herbicidal compositions of the present invention can be easily determined by a person skilled in the technical field.

A preferred method for producing the stable herbicidal granules or powder of the present invention, which may have a high content of an integral adjuvant, involves taking the mixture obtained in step 3 of the production method described herein and spray drying it to obtain a stable powder of the present invention, which can then be further processed into stable granules using a low shear granulation method such as disk granulation fluidized bed agglomeration or spray agglomeration. The use of such processing methods with a low shear rate is necessary to minimize mechanical damage to the granules and the loss of an integral aid.

Another aspect of the present invention relates to the addition of one or more pesticidally active ingredients, plant growth regulators or antidotes to the solid herbicidal compositions of the present invention. These pesticidally active ingredients, plant growth regulators, and antidotes may include one or more of a herbicide, insecticide, fungicide, plant growth regulator, or herbicidal antidote.

Suitable herbicides that can be added to the solid herbicidal compositions of the present invention include clodinafop-propargyl, celodime, cycloxydim, diclofop-methyl, phenoxaprop-ethyl + isoxydiphenyl-ethyl, pinoxaden, sentoxime, heat-oxide, tralcoxime, 2 esters and 4-D, 2,4-MCPA, esters and amines of 2,4-MCPA, acetochlor, acifluorfen,

- 6 022128 alachlor, amidosulfuron, aminopyralide, aminotriazole, ammonium thiocyanate, aniliphos, benfuresate, bentazone, bentazone sodium, bentiocarb, benzobicyclone, benzofenap, bifenox, chlorpromonofluorobromonfluorobromonitrofen chloride cinosulfuron, clomazone, clomeprop, clopyralide, cumiluron, daimuron, diflufenican, dimepiperate, dimetamethrin, diquat, dithiopyr, ЕК2612, ЕРТС, esprocarb, ET-751, etbenzanfenfenfluzfenfamfenfluzamenfenfluzfenfamfenfluzamfenfenfluzamfenzo flupirsu lfuron, fluroxypyr, esters and salts of fluroxypyr, fomesafen, foramsulfuron, glufosinate, glufosinate-R, glyphosate, imazametabenz, imazapik, imazapyr, imazakvin, indanofan, ioxinyl, ipfencarbosone methenol, moxoxynil, ipfencarbosone methenolamine, isofoxene, mofoxanaborzenone, moxoxinyl, ipfencarbazone methenolazone, isoformone monosulfuron, ΜδΜΑ, orthosulfamuron, oryzaline, oxadieargyl, oxadiazone, oxazichlomephone, oxyfluorfen, paraquat, pendimethalin, pentoxazone, petoxamide, picloram, piperofos, pretilachlor, prohexadione calcium, propachisulfonum, propanchloride, propanchloride, propane irabutikarb, piraklonil, pirazogil, pirazolinat, pyrazoxyfen, pyribenzoxim, pyridate, pyriftalid, pyriminobac-methyl, pyrimisulfan, kvinoklamin, quinclorac, δ-3252, simazine, simetryn, S-metolachlor, sulcotrione, sulfentrazon, sulfosate, tefuryltrione, thenylchlor, thiazopyr, thiobencarb, triafamon, triclopyr, triclopyr esters and amines, trifluralin, trinexapac-ethyl and tritosulfuron.

Suitable insecticides that can be added to the solid herbicidal compositions of the present invention include abamectin, acephate, acetamipride, acrinatrin, alpha-caspermethrin, alpha-endosulfan, azadirachtin, azinfos-ethyl, azinfos-methyl, bendiocarb, benfisulfarbene, benfurfarcarb, benfurfarpar beta-cypermentrin, bifentrin, bufencarb, buprofesin, butacarb, cadusafos, carbaryl, carbofuran, carbosulfan, kartap, kartapa hydrochloride, chlorantraniliprol, chlorfenapyr, chlorfenvinfos, chlorfluazuron, chlormefos, chlorpyrifif, chlorpyrifif, chlorpyrifif omafenoside, clothianidin, cyanthraniliprol, cyfluthrin, cygalotrin, cypermethrin, deltamethrin, diazinon, dicrotofos, diflubenzuron, dinotefuran dimethoate, disulfofon, emamectin, ethamefenfenfenfenfenfenfenfenfenfenfenfenfenfenfenfenfenfenfenfenfenfenfenfenfenfen methyl, etofenprox, fenamiphos, phenazaflor, fenetacarb, fenitrotion, phenobucarb, fenpropatrin, fensulfotion, fenthion, fenthion-ethyl, fenvalerate, fipronil, flonikamide, flubendiamide, flucytrinate, phonofosum, gamfenfamot, gamfenofigot, gamfenofigot, gamfenofid enproks, halofenozide, heptenophos, gikvinkarb, imidacloprid, indoxacarb, Isazofos, izobenzan, izokarbofos, isofenphos, isofenphos-methyl, isoprocarb, izotioat, isoxathion, kinoprene, lambda-cyhalothrin, lepimektin, lufenuron, malathion, methamidophos, methomyl, methoxyfenozide, mevinphos, mexacarbate, milbemectin, monocrotophos, nitenpyram, novaluron, omethoate, oxamyl, oxydemetone-methyl, oxydeprofos, oxydisulfotone, parathion, parathion-methyl, penfluuron, permethrin, fentoate, forate, phosphonosome, phosphiriphosphamide, phospholiphosphamide, phosphiriphosphamide, phospholiphosphamide, phosphiriphosphamide, phosphiriphosphamide, phosphiriphosphamide, phosphoriphosphonamide -ethyl, pyrimifos-methyl, primidophos, profenofos, proflutrin, promecarb, propafos, propoxur, prothiophos, pymetrozine, pyrafluprol, pyridyl, pyrifluquinazone, pyriprol, pyriproxifen, spinetrofenfludoroflufetrofetrofetrofetrofetrofetrofetrofetroflufin, , teflutrin, tetramethylflutrin, tetracypermethrin, thiacloprid, thiamethoxam, tikrofos, thiocyclam, thiocycl oxalate, thiodicarb, thiometon, thiosultap, thiosultap disodium, thiosultap monosodium, turingienzurum, trifen triphin, tolfen he and zeta cypermethrin.

Suitable fungicides that can be added to the solid herbicidal compositions of the present invention include tricyclazole, phthalide, carpropamide, pyroquilone, diclocimet, phenoxanil, probenazole, isoprothiolan, iprobenfos, isothianyl, thiadinyl, casugamycin, polynamycin, valutamycin, valutamycin, calciton, flutamicin, valutamycin, fluticin, flutamicin, flutamicin, valutamycin, flutamicin, flutamycin, flutamycin, calcitron, calipon, and toclofos-methyl, boscalide, pentiopyrad, tiflusamide, bixafen, fluopyram, isopyrazam, propiconazole, diphenoconazole, fenbuconazole, ipconazole, triadimefon, hexaconazole, azoxystrobin, metaminostrobin, arizibenzene and lar-8-methyl. Some of these fungicides may not be effective in controlling disease when applied during application of a granular herbicide, since the propagation of the fungus causing the disease and its growth cycles may not coincide with the growth cycles of the target weeds. The effective application and time of application of these fungicides can be easily determined by a person skilled in the art.

Suitable herbicidal antidotes which can be added to solid herbicidal compositions of the present invention include benoxacor, benthiocarb, klokvintoset-mexyl, daimuron, dichlormid, ditsiklonon, dimepiperate, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, protein garpin, izoksadifen- ethyl, mefenpyr diethyl, mefenate, MS 191, ΜΟΝ 4660, naphthoic anhydride (HA), oxabetrinyl, K29148, and Ν-phenyl-sulfonylbenzoic acid amides.

Suitable plant growth regulators that can be added to the solid herbicidal composition of the present invention include 2,4-D, 2,4-ΌΒ, ΙΑΑ, ΙΒΑ, naphthalene acetamide, α-naphthalene acetic acid, kinetin, zeatin, ethephon, aviglycine, 1-methylcyclopropene (1-MCP), ethephone, gibberellins, gibberellic acid, abscisic acid, ancimidol, flurprimidol, mefluidide, paclobutrazole, tetcyclacis, uniconazole, brassinolide, brassinolide-ethyl and ethylene.

In addition to the compositions and uses formulated above, the present invention also encompasses the composition and use of solid herbicidal compositions in combination with one

- 7,022,128 or more additional compatible ingredients. Other additional compatible ingredients may include, for example, one or more agrochemically active ingredients, surfactants, coloring agents, fertilizers and micronutrients, pheromones, and many other additional ingredients having functional utility, such as, for example, stabilizers, odorants and dispersants agents. When the compositions of the present invention are used in combination with additional active ingredients, the compositions patented by the present disclosure may be formulated with another active ingredient or active ingredients in the form of solid herbicidal compositions, tank mixtures in water with another active ingredient or active ingredients for use by spraying or can be applied sequentially with another active ingredient or active ingredients by separately adding to tv Atom form or by spraying.

In addition, the solid herbicidal compositions of the present invention may optionally be mixed with other solid compositions containing additional active ingredients to form a composition comprising, for example, a physically uniform mixture of granules or a physically uniform mixture of powders. This mixture of solid compositions can be used to control undesirable plants in aquatic environments such as flooded rice fields and fields.

Surfactants traditionally used in the field of formulation technology and which may optionally be used in the present compositions are described, inter alia, in the MSSSNeogo EsUgdshx apb EtiIpege Appia1, MS RiNkIpd Coag., Ridgewood, New Jersey, 1998 and Epsus1oreLa oG 8igGas1ap15. νοί. Ι-ΙΙΙ, CHet1ca1 Reykdy Co., New York, 1980-81. These surfactants can be anionic, cationic or nonionic in nature and can be used as emulsifying agents, wetting agents, suspending agents, or for other purposes. Typical surface active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; alkylarylsulfonate salts such as calcium dodecylbenzenesulfonate; alkyl phenol and alkylene oxide addition products such as non-phenyl C ₄₈ ethoxylate ethoxylate; soaps such as sodium stearate; alkylnaphthalene sulfonate salts such as sodium dibutyl naphthalene sulfonate; dialkyl esters of sulfosuccinate salts, such as di (2 ethylhexyl) sulfosuccinate; quaternary amines such as lauryltrimethylammonium chloride; block copolymers of ethylene oxide and propylene oxide; salts of esters of mono- and dialkyl phosphates.

Often, some of these surfactants can be used interchangeably as an agricultural adjuvant, as a liquid carrier, or as a surfactant.

The following examples illustrate the present invention.

Example 1. Obtaining granules of the present invention containing cygalofop-butyl, dried in an oven on a flat disk.

The oil phase is obtained by dissolving 1.8 g of cyhalofop-butyl in 43.2 g of methyl soyoate (Adpscie OME 188-I; registered trademark Sodtk). The aqueous phase is obtained by dissolving 32 g of sucrose, 10 g of a 20% (w / w) solution of CeKo1® 205 (polyvinyl alcohol; trademark 8ek18sh Сёка1 Co., IG) in water and 21 g of sodium lignosulfonate (Votgekregee® ΝΑ; registered trademark Voggedaagb ПппоТесЬ) in 71 g of water. Then, the oil phase is slowly added to the aqueous phase with simultaneous stirring with a 8P1 'eG5op agitator with a high shear rate for 30 minutes at about 11000 rpm to obtain a mixture of dispersed oil droplets in water with an average volume diameter of 1-2 microns. As soon as the desired droplet size is reached, the mixture is dried on a flat disk in an oven at 60 ° C to obtain dried solid granules A (Table 1) with a residual water content of 2 to 3 wt.% Relative to the total weight of the sample. The average volumetric diameter of the solid particles obtained from granules A has a range of 2 to 4 μm after re-dispersion in water. In a manner similar to that described in the present description, granules B and C are also obtained (Table 1).

Table 1

The granule composition of the present invention

Ingredients Sample ID Granules A Granules B Granules C mass% mass% mass% cygalofop butyl eighteen 3, 6 5,4 methylsoyat 43,2 41,4 39, 6 sucrose 32 32 32 VSGGregreg® ΝΑ 21 21 21 Ce1Uo1® 205 2 2 2

Example 2. Obtaining granules of the present invention containing pencules, bensulfon-8 022128 ron-methyl, phenoxaprop-P-ethyl, compound A, azimsulfuron or imazosulfuron.

Granules Ό, E and C.

Using the ingredients shown in table. 2, aqueous suspension concentrates (8C) containing the active ingredients are obtained by shaking overnight 25% suspensions of solid particles containing the technical active ingredient. You can! Ό425 and P1igoshs P105, in plastic bottles with a volume of 20 ml in the weight ratio shown in the table. 2, and containing steel balls weighing 9-10 times the mass of 25% suspensions of solid particles. The aqueous phase is obtained by dissolving 1 g of sucrose, 10 g of a 20% (w / w) solution of Ce1uo1® 205 (polyvinyl alcohol; trademark 8ek1ksh Sketka1 Co., I4.) In water and ~ 51.7 g of sodium lignosulfonate (Voggekregke ® ΝΑ; registered trademark of Voggeda Пy PodioTes) in 96 g of water. Then the oil phase (for example, 44 g methyl methyl soyat - Adchtsie® ME 188-I; registered trademark Sodshk) is slowly added to the aqueous phase with simultaneous stirring with a §Puegkoy mixer with a high shear rate for 30 minutes at about 11000 rpm, to get a mixture of dispersed oil droplets in water with an average volume diameter of 1-3 microns. As soon as the desired droplet size is reached, the active ingredient suspension concentrate is added to the mixture to obtain a final aqueous mixture containing 1 g of the active ingredient. After gently mixing with a low shear rate (1000-2000 rpm) using a mixer § Puegkoy or ΙΚΑ the aqueous mixture was dried by spraying in a VISN1 190 dryer for spraying with an inlet temperature of 135 ° C and an outlet temperature of 90 ° C at a feed rate 300 ml / h to obtain a solid powder with a residual water content of 2 to 3 wt.% Relative to the total weight of the sample. The spray dried powder was granulated using a domestic mixer (B1ask ap4 Eskeg Nap4u Skorreg HC2000) and 12 wt.% Water as a binder. The blades of a household mixer are wrapped with plastic tape to reduce the shear effect of the blades on the powder, dried by spraying. The final product is obtained by drying the granules at 30-50 ° C until then, until the total humidity reaches 3% by weight of the sample.

Granules R.

Using the ingredients shown in the table. 2, the aqueous phase is obtained by dissolving 1 g of sucrose, 10 g of a 20% (w / w) solution of Ce1uo1® 205 (polyvinyl alcohol; trademark 8ek1ksh Sketuya1 Co., L4.) In water and 51.95 g of sodium lignosulfonate ( Voggekregke® ΝΑ; registered trademark of Voggedaage PdioTesk) in 96.5 g of water. The oil phase is obtained by dissolving 1 g of phenoxaprop-Retyl in 44 g of methyl soyoate (Adtsiee® ME 188-I; registered trademark Sodshk). Then, the oil phase is slowly added to the aqueous phase with simultaneous stirring with a ZIuegkoi mixer with a high shear rate for 30 minutes at approximately 11000 rpm to obtain a mixture of dispersed oil droplets in water with an average volume diameter of 1-3 μm. As soon as the desired droplet size is reached, the aqueous mixture is dried by spraying in the BISN1 190 dryer for spraying with an inlet temperature of 135 ° C and an outlet temperature of 90 ° C at a feed rate of 300 ml / h to obtain a solid powder with a residual water content of 2- 3 wt.% Relative to the total weight of the sample. The powder is granulated using a domestic mixer described in the present description, and 12 wt.% Water as a binder component. The blades of a household mixer are wrapped with plastic tape to reduce the shear effect of the blades on the powder, dried by spraying. The final product is obtained by drying the granules at 30-50 ° C until then, until the total humidity reaches 3% by weight of the sample.

Granules H and Ι.

Using the ingredients shown in the table. 2, suspension concentrates containing the active ingredients are obtained by mixing 2 g of commercial granules with the active ingredient content of 50 wt.% (For example, Vga // ok \ US and composition CuShueg \ US) in 8 g of water with each ~ 20% suspensions of solid particles, respectively. The aqueous phase is obtained by dissolving 1 g of sucrose, 10 g of a 20% (w / w) solution of Ce1uo1® 205 (polyvinyl alcohol; trademark 8ek1ksh Sketuya1 Co., I4.) In water and ~ 51 g of sodium lignosulfonate (Voggekregke ® NΑ; registered trademark of Voggedaad PdioTesk) in 95 g of water. Then, the oil phase (for example, 44 g methyl methyl soyad - Adhcie® ME 188I; registered trademark Sodshk) is slowly added to the aqueous phase while stirring with a stirrer § Puegkoy with a high shear rate for 30 minutes at about 11000 rpm to obtain a mixture of dispersed oil droplets in water with an average volume diameter of 1-3 microns. Once the desired droplet size is achieved, the active ingredient suspension concentrate is added to the mixture to obtain a final aqueous mixture containing 1 g of the active ingredient. With weak stirring at a low shear rate (1000-2000 rpm) using a §Puegkoy or 1KA mixer, the aqueous mixture is dried by spraying in a VISN1 190 dryer for spraying with an inlet temperature of 135 ° C and an outlet temperature of 90 ° C at a feed rate 300 ml / h to obtain a solid powder with a residual water content of 2 to 3 wt.% Relative to the total weight of the sample. The powder is granulated using a domestic mixer described in the present description, and 12 wt.% Water as a binder component. Shovels of a household mixer

- 9 022128 is wrapped in plastic tape to reduce the shear effect of the blades on the powder, dried by spraying. The final product is obtained by drying the granules at 30-50 ° C until then, until the total humidity reaches 3% by weight of the sample.

table 2

The ingredients used to obtain the granules of this

Entries from these commercial products.

² Woghekgreke ΝΑ (sodium lignosulfonate) serves as a balanced ingredient.

Example 3. Obtaining granules and powders of the present invention containing cygalofopbutyl.

Spray dried powder.

Using the ingredients and relative amounts shown in the table. 3, four spray dried powders of the present invention were prepared as described. The oil phase of an oil-in-water emulsion is obtained by dissolving cyhalofop-butyl in methyl soyate in the desired proportions. The aqueous phase, 3 times greater in weight than the oil phase, is obtained by dissolving sucrose, a 20% aqueous solution of polyvinyl alcohol (Ce1uo1® 205; §ek1ksh Seshka1 Co., Yb.) And sodium lignosulfonate (Woggekregke® ΝΑ; idio ! es, 1ps.) in water. The oil phase is slowly added to the aqueous phase with simultaneous stirring with a Zbuegkop mixer with a high shear rate for 30 minutes at about 11000 rpm to obtain a highly dispersed emulsion containing oil droplets with an average volume diameter of 1-2 microns. Once the desired particle size of the emulsion is achieved, the oil-in-water emulsion is dried using a spray dryer (Visa Model 290), operating at inlet and outlet temperatures of 135 and 85 ° C, respectively, and at a liquid flow rate of 300 ml / h. The average volumetric diameter of the dried powder obtained from spray drying, after repeated dispersion in water, ranges from 2 to 4 microns. The spray dried powder disintegrates rather quickly (in 1 min) in water due to the instant dissolution of sucrose and sodium lignosulfonate.

- 10 022128

Table 3

The composition of the powders of the present invention obtained by spray drying

Ingredients Sample ID Powder A Powder in Powder FROM Powder ϋ mass% mass% mass% mass% cygalofop butyl 1.35 2.7 1.35 1.80 impurities 0.05 0.1 0.05 0,07 methylsoyat 43, 6 42, 2 43, b 43.13 sucrose 32 32 10 one lignosulfonate sodium 21 21 43 52 polyvinyl alcohol 2 2 2 2

Granules obtained by granulation with a low shear rate.

The Reggo-1ESB disk granulator (16 '' diameter) was used for disk granulation. 2 kg of spray dried powder C was loaded onto a disk at a feed rate of 200 g / min. The disk angle was set to 45 ° and the disk speed was set to 26 rpm. Water was continuously sprayed onto the powder during the rotation of the disk so that the final moisture content in the finished granules was 6 wt.%. The finished granules were then dried in an oven in trays at 40 ° C. overnight and then sieved through a sieve column to remove any too small and too large granules. During granulation, no oil phase was detected. The dried granules remained stable during storage stability testing at 54 ° C for 4 weeks and did not show a significant change in the size of the emulsion droplets after repeated dispersion in water before and after storage stability testing. During stability studies, no sintering or separation of the oil phase was observed. The granules showed good fluidity, and the rheological properties remained unchanged after testing for storage stability. The granules showed good re-dispersibility after dilution in water and dispersed for 3 minutes without any shaking. The granules also showed similar re-dispersibility after storage at 54 ° C. for 4 weeks. Up to 5 wt.% Hydrophilic silica can be used as an additive in processing to improve the flow / anti-sintering of the final granules. The granules listed in the table. 4 was obtained by granulation at a low shear rate in a manner similar to that described herein.

Table 4

The composition of the granules of the present invention obtained by granulation with a low shear rate

Ingredients Sample ID Pellets 0 Granules K Granules b mass% mass% mass% cygalofop butyl 1, 80 3.6 5,4 impurities 0,07 0, 13 0.2 methylsoyat 43.13 41.27 39,4 sucrose one one one sodium lignosulfonate 52 52 52 polyvinyl alcohol 2 2 2

Granules obtained by agglomeration in a fluidized bed.

For granulation processing, the ORSO-1 semi-industrial fluidized-bed granulation device (manufactured by O1a11) was used. 800 g of powder C was placed in a granulator chamber. The water spray rate was set at 15 g / min. The temperature of the incoming air was set at 30 ° C. Water was sprayed for 5 min at a speed of 15 g / min.

Then, the water spray rate was reduced to 13 g / min and spraying was continued until the water content accumulated in the agglomerates was 400 g. The agglomerates were dried at an inlet air temperature of 40 ° C for a total period of 8 minutes and then unloaded. The obtained granules were sieved through a sieve column with openings of 12, 14, 20, 30 and 50 mesh. Fractions with a preferred size of -12 / + 14 mesh and -14 / + 20 mesh were collected. Size fraction output

- 11,022,128 +50 mesh was significantly lower compared to the -12 / + 14 mesh fraction, indicating successful agglomeration. Release of oil from the granules was not observed. The granules can be further dried in an oven to the desired moisture level before storage.

Granules obtained by agglomeration by spraying on a fluidized bed.

Using a multi-dryer Legota Is ΜΡ 1 with a fluidized bed (CEL Pagta 8uk! Etk; lower diameter 20 cm) with a nozzle in position 4 (70 cm above the sieve), a spray rate of 25 g / min and a fluidized bed temperature of 68 ° C were used to obtain a sample of granules K weighing 3 kg from an aqueous mixture containing 48.6 wt.% solid particles having the composition described in table. 4 (for K granules). The obtained granules had a bulk density of 580 g / l, where 78.4 wt.% Of the granules had a size> 1250 μm.

Example 4. The use of granules A, B and C for weed control in model rice receipts.

Creation of model rice receipts.

kg of mineral soil and 500 ml of distilled water were added to a container (4.163 L (1.1 gallons) round ΗΌΡΕ container 15 cm in height 20.55 cm in diameter; for processing purposes, the surface area was calculated to be 331 cm ² with an equivalent of 1 ha of 10 ⁸ cm ² ) and thoroughly mixed with a spatula for 5 min to obtain a smooth soil paste. As soon as the mixture was obtained, a 3-cm furrow was made through the middle of the container into which 18 g (0.6 ounces) of Oktoso1e® product (registered trademark of 8 Soyk Sotrapu LС or its branches; 17: 6: 10 Ν: Ρ: Κ was added ) The furrow was then sealed, leaving Octoso® below the level of the soil surface.

Germination of plants.

A weed plant is Chinese leptochloe, Epilosophyllus lycophea (Epersian).

To obtain a viscous slurry in a small container, 80 g of mineral soil was mixed with 40 ml of distilled water. To the sludge was added / / ₄ teaspoons (2-4000) of Lep1osl1oa seeds and mixed thoroughly to evenly distribute the seeds. Approximately 3 g of this slurry was placed on the surface of the finished paste on one side of each container and distributed in a thin layer in the form of a strip 1-2 cm wide from edge to edge of the container. This gave 25-50 plants in each container. Transparent stretch film was used to cover containers acting as greenhouses. The film was left in place with adhesive tape until germination of the seed Lep1osl1oa for 5 days. Covered tanks were kept in a greenhouse at a constant temperature of 18-22 ° C and a relative humidity of 50-60%. Natural light was provided by metal halide ceiling lamps with a power of 1000 W with an average illumination of 500 μE-m ^-2 -s ^-1 photosynthetically active radiation (PAR). The daylight hours were 16 hours.

A weed plant is a brambleberry, Esopposia sigik-daSh (ESNSS).

As soon as the seed of the leptochloe sprouted, a small depression was made on the paste parallel to the leptochlois.

Blackberry seed was distributed along this trench and then covered with white sand.

This produced approximately 20-30 plants in each tank. At this stage, plant material was watered from above with distilled water and kept very moist. The tanks were moved to a warmer greenhouse, where the temperature was maintained at 26-28 ° C with the same lighting parameters as described for Chinese leptochloe.

Cereal plant - raw rice, Ogu / a kayua kykr. 1aroshsa, grade M202 (ΟΚΥ81).

On the same day that the blackberry was planted, rice was also sown directly in the pot of soil paste, following the same method. A small indentation was made in the soil paste parallel to the Chinese and blackberry mite, and the seeds were distributed along this trench, then covered with white sand. It should also produce approximately 20-30 plants in each tank.

Plants were allowed to grow until they reached a height of 6-8 cm for 8 days.

Flooding and methods of application in checks for the assessment of herbicides.

As soon as the plants reached the proper size (the growth stage of various species varied from 2 to 4 leaves), the containers were poured with distilled water, creating a depth of 3 cm, leaving 1-2 cm of each plant above the surface of the water. Herbicidal treatments were applied directly to the water in the check in the form of granular or liquid compositions at application rates corresponding to surface area. Treatments were repeated 2-3 times. In the intervals of assessment, the percentage of visible damage and destruction of weeds was made on a scale from 0 to 100% compared to untreated control plants (where 0 corresponds to the absence of damage or destruction and 100 corresponds to the complete death of the plant).

- 12 022128

Table 5

The stability of crops and the percentage destruction of weeds using granules with cygalofop-butyl according to the present invention 21 days after application in the test on model rice checks in the greenhouse

Active herbicidal ingredient (s) Description processing Norm making (gai / ha) Middle % damage to plants οκγεσ EJES ECNSS cyaglofop-butyl Granule A 45 0 0 89 90 0 fifteen one hundred 180 0 63 one hundred 360 0 one hundred one hundred

cyaglofop-butyl Granule B 45 0 twenty 95 90 0 40 90 180 0 40 98 360 0 90 one hundred cyaglofop-butyl Granule C 45 0 thirty 92 90 0 95 85 180 0 one hundred one hundred 360 0 one hundred one hundred cyaglofop-butyl SIPSNEG® CA ¹ 45 0 5 5 90 0 10 10 180 0 40 45 360 0 95 75

¹ С11псНег® СА (registered trademark 1) o \ y Adgo8s1epse§ bC) is an EC composition containing 285 g of cyhalophop-butyl per 1 liter.

Example 5. The use of granules of the present invention containing pencules, bensulfuron methyl, phenoxaprop-P-ethyl, compound A, azimsulfuron or imazosulfuron for weed control in model rice fields.

Creation of model rice receipts.

Distilled (ΌΙ) water and crushed soil from the top layer of the profile are added to the standard cement mixture in a volume ratio of 1: 1 and mixed well to obtain a smooth soil paste. The moisture content of the soil paste can be checked as follows using a round flat disk of non-hygroscopic hard plastic with a diameter of 15 cm.

380 ml of soil paste in the center of the plastic disc. Soil paste at the desired humidity should be distributed in such a way as to fit exactly into the circle. If the soil paste extends beyond the perimeter of the circle, then it is too wet and more soil should be added to the soil paste from the top layer of the profile. If the soil paste is not distributed so that it fits completely into the circle, then it is too dry and more ΌΙ of water must be added to the soil paste. Correct the ratio of soil from the top layer of the profile to the water until the correct moisture is reached, as described. A 1 _^1/2 teaspoon product O5toso1e® (registered trademark 8soy8 Sotrapu S or its affiliates; 17: 6: 10 Ν: Ρ: Κ) is added to the container bottom (4,163 liters (1.1 gallons), a round container 15 from ΗΌΡΕ cm in height 20.55 cm in diameter; for processing purposes, the calculated surface area is 331 cm ^{2 * * * * *} , with the equivalent of 1 ha 10 ⁸ cm ² ) and then 2750 ml of soil paste is added to the container, filling it halfway. In each container, slats are horizontally stacked to create separate areas, in each of which different types of plants can be grown.

- 13 022128

Germination of a plant.

Weed plant - monochoria, Moposka uad1pakk (MOOUA).

In a small container, 80 g of mineral soil was mixed with 80 ml of distilled water to obtain a viscous slurry. _^1/2 teaspoon monochoria seed was added to the slurry and thoroughly mixed to distribute the seed uniformly. Approximately 3 g of this sludge was placed on the surface of the resulting soil paste in one sector of each container and distributed in a thin layer within a strip 1-2 cm wide from edge to edge of the container. This gives 30-50 plants in each container. Transparent stretch film was used to cover containers acting as greenhouses. The film was left in place with adhesive tape until the seeds of the monochoria sprouted for 7 days. Covered containers were kept in a greenhouse at a constant temperature of 28-32 ° C and a relative humidity of 50%. Natural light was provided by metal halide ceiling lamps with a power of 1000 W with an average illumination of 500 μE-m ^-2 -s ^-1 photosynthetically active radiation (PAR). The daylight hours were 16 hours.

A weed plant is a blackberry, Ec1yposk1oa sgik-daSh (ESNSS).

The bilberry was soaked in ΌΙ water for 24 hours, washed and allowed to drain before planting in order to remove growth inhibitors and enhance germination. As soon as the seeds of monochoria sprouted, the seeds of the blackberry were distributed in the section intended for it, covered with 2 cm of finely dispersed mineral soil sifted through sieves with holes with a diameter of 18 mesh, and marked for identification. This gives approximately 20-30 plants in each container. At this stage, the plant material was covered with a transparent stretch film acting as a greenhouse until the plants began to germinate. The coating was removed as soon as the blackberry began to emerge. The plants were grown in a greenhouse, where the temperature was maintained at 28-32 ° C under the same lighting parameters as described for monochoria. The plants were allowed to grow until they reached a height of 5-9 cm for 8 days.

A weed plant is a peasant bramble, Esopposkoyo sopit (ECNSO).

The peasant bilberry was soaked in ΌΙ water for 24 hours, washed and allowed to drain before planting in order to remove growth inhibitors and enhance germination. As soon as the seeds of monochoria sprouted, the peasant blackberry was distributed in the section intended for it, covered with 2 cm of finely dispersed mineral soil sifted through a sieve with holes with a diameter of 18 mesh, and marked for identification. This gave approximately 20-30 plants in each container. At this stage, the plant material was covered with a transparent stretch film acting as a greenhouse until the plants began to germinate. The coating was removed as soon as the peasant blackberry began to emerge. The plants were grown in a greenhouse, where the temperature was maintained at 28-32 ° C with the same lighting parameters as described for monochoria and blackberry. The plants were allowed to grow until they reached a height of 5-9 cm for 8 days.

As soon as the plants reached the proper size (the growth stage of various species ranged from 2 to 4 leaves), the containers were poured with distilled water, creating a depth of 3 inches, immersing the plants in water by 80-100%. The height of the outside of each container was measured and a 3-inch line of the level of flooding was marked with a black marker to avoid differences in water levels. The granules were pre-weighed based on the rate of application of the active ingredient per unit area, placed in 30 ml tubes and closed. Herbicidal treatments were applied directly to water in rice fields in the form of granular compositions. Treatments were repeated 3 times. Assessment of visible damage and destruction of weeds as a percentage was carried out on a scale from 0 to 100% on specific days after application compared to untreated control plants (where 0 corresponds to the absence of damage or destruction and 100 corresponds to the complete death of the plant).

- 14 022128

Table 6

The destruction of weeds in percent using the granules of the present invention 21 days after application in the test on model rice checks in the greenhouse

Active herbicidal ingredient (s) Description processing Norm making (gai / ha) Average% damage to plants ΜΟΟΥΑ ECNSS ECSO Pencussulam Granule O 10 one hundred 73 77 twenty one hundred 92 87 bensulfuron-me Granule E 17.5 98 thirteen thirty 35 99 75 55 70 one hundred 85 70 phenoxalrop-R-Et Granule G 21, 5 one 58 one hundred 43 8 one hundred one hundred 86 82 one hundred one hundred Compound A Granule C 25 one hundred 28 70 fifty one hundred 90 one hundred one hundred one hundred one hundred one hundred cyaglofop-butyl X6A-244 4 ¹ 75 0 52 57 150 0 80 77 300 10 one hundred one hundred

¹ KHOL-2444 is a granular composition KS1 containing 18 g / kg of cygalofopbutyl and 115 g / kg of the oil-derived auxiliary agent ditridecyl phthalate (C1teyeg®1KO from Νίρροη Kauaki Co., G-14 .. Japan).

Table 7

The destruction of weeds in percent using the granules of the present invention 15 days after use in the test on model rice checks in the greenhouse

Active herbicidal ingredient (s) Description processing Application rate (gai / ha) Average% damage to plants ΜΟΟνΑ. ECSO azimsulfuron Granule H 17.5 nt ^one 72 35 nt * 94 imazosulfuron Granule I 45 95 96 90 90 98

¹ nt = Test not performed.

Example 6. The use of granules of the present invention containing cygalofop-butyl for weed control in rice fields in the field.

Field tests were carried out on rice using a standard methodology for the study of herbicide in a small area. On a plot of 2 m ² in size, rings with a diameter of 1.6 m were used, placed in the soil of a rice check with the possibility of flooding. Each treatment was performed in 3 replicates. Rice crops were grown using normal cultivation methods for fertilizing, sowing, watering, flooding and maintaining to ensure good growth of crops and weeds in the conditions of sown rice in Taiwan.

Rice was a Japanese type that was sown directly into the soil rings of rice checks. Before applying the treatment, the soil in the rings was maintained in a water-saturated state. When the treatment was performed, the rings were filled with water, creating a depth of 3-7 cm. The processing time was chosen at the stage of forming 1-3 leaves of the blackberry. The amount of application during processing was calculated based on the specific application rate based on the area. The treatments were applied to the soils in the rings of rice fields manually and the depth of water in the rings was maintained at 3-7 cm after applying the treatments 15 022128 ki. Treatments were evaluated in comparison with untreated control plots. The apparent destruction of weeds was evaluated on a scale from 0 to 100%, where 0 corresponds to the absence of damage and 100 corresponds to complete destruction.

Tab. Figure 8 shows the biological effectiveness of various treatments in applications by spreading rice checks directly in water in the form of granular compositions. Test tests were carried out on raw rice plants (OKU8A), leptochloe (LERSN) and blackberry (ECNSS), and different application rates of cyhalofop-butyl were applied. This test on flooded rice fields included comparative processing using a commercial granular composition of cygalofop-butyl (Cl2b2b®1CO). Application rates were based on the amount of active ingredient applied per hectare (gai / ha) in grams.

Table 8

The stability of crops and the percentage destruction of weeds using the granules of the present invention after 28 days after application in the test on rice fields in the field

Active herbicidal ingredient (s) Description processing Application rate (g ai / ha) Average% damage to plants ΟΒ.Υ3Ν LESC ECNSS Cigalofop butyl Granule L one hundred 0 one hundred 99 150 0 one hundred one hundred 225 0 one hundred one hundred 300 0 one hundred one hundred Cigalofop butyl Granule K one hundred 0 99 85 150 0 one hundred 92 225 0 one hundred one hundred 300 0 one hundred one hundred Cigalofop butyl Granule b one hundred 0 93 thirteen 150 0 97 thirty 225 0 99 94 300 0 one hundred 96 cyaglofop-butyl HSA-2444 ¹ one hundred 0 95 85 150 0 97 90 225 0 one hundred 94 300 0 one hundred 98

¹ HOA-2444 is a granular composition KC1 containing 18 g / kg of cygalofopbutyl and 115 g / kg of the oil-derived adjuvant ditridecyl phthalate (SNPSYEG® 1KO from Mrop Kauaki Co., Ι, ΐά., Japan).

Example 7. The use of the powders of the present invention to obtain aqueous mixtures for spraying and their use for applying to foliage by spraying to control weeds in rice fields in the field.

Field tests were carried out on rice using a standard methodology for the study of herbicide in a small area. On a plot of 1 m ² in size, rings with a diameter of 0.56 m were used, placed in the soil of a rice check with the possibility of flooding. Each treatment was performed in 3 replicates. Rice crops were grown using normal cultivation methods for fertilizing, sowing, watering, flooding and maintaining to ensure good growth of crops and weeds in the conditions of sown rice in Taiwan. Rice was a Japanese type that was sown directly into the soil rings of rice checks. Before applying the treatment, the soil in the rings was maintained in a water-saturated state. The processing time was chosen at the stage of formation of 3-4 blackberry leaves. The treatments were applied by spreading the foliar treatment with a back sprinkler at a pressure of 30 psi. Two nozzles using TEE 1ET - 1101 L at a distance of 50 cm were used for foliar application to completely cover each of the annular sections. The application rate was 450 l / ha. The amounts for the treatment used were calculated on the basis of specific application rates based on 16,022,128 ve areas. The water depth at the sites in the rings was re-established at the level of 7-10 cm 24 hours after foliar application.

Tab. Figure 9 shows the biological effectiveness of the spraying process using aqueous mixtures obtained from powder A and powder B. Test tests were carried out on raw rice (ΟΚΥδΤ), leptochloe (LERSN) and blackberry (ECNSS) plants, and different application rates of cyhalofop-butyl were applied. This test on flooded rice fields included comparative processing using a commercial EC composition of cygalofop-butyl (Cl2b2b®100EC). Application rates were based on the amount of active ingredient applied per hectare (gai / ha), in grams.

Table 9

Sustainability of crops and percent destruction of weeds using water mixtures for spraying with cygalofop-butyl,

¹ Sypsel® 100ES (registered trademark 1) o \\ · Α§ ^ o8c ^ enseδ bC) is an EC composition containing 285 g of cyhalophop-butyl per 1 liter.

Claims (29)

CLAIM 1. A stable herbicidal composition of the granules, containing an essential adjuvant, which includes: a) a herbicidally active ingredient selected from the class of acetyl-CoA carboxylase or ALS enzyme inhibitors, ranging from 1 to 200 g / kg to the total weight of the composition; b) an integral adjuvant, comprising from 50 to 750 g / kg in relation to the total weight of the composition; c) solid carbohydrate constituting from 10 to 700 g / kg with respect to the total weight of the composition; b) a solid water-soluble polymer or oligomer constituting from 50 to 700 g / kg with respect to the total weight of the composition, provided that the solid carbohydrate and solid water-soluble polymer or oligomer must be at least 200 g / kg total compositions. 2. A robust herbicidal powder composition comprising an essential adjuvant which includes: a) a herbicidally active ingredient selected from the class of acetyl-CoA carboxylase or ALS enzyme inhibitors, ranging from 1 to 200 g / kg to the total weight of the composition; b) an integral adjuvant, comprising from 50 to 750 g / kg in relation to the total weight of the composition; c) solid carbohydrate constituting from 10 to 700 g / kg with respect to the total weight of the composition; b) a solid water-soluble polymer or oligomer constituting from 50 to 700 g / kg with respect to the total weight of the composition, provided that the solid carbohydrate and solid water-soluble polymer or oligomer must be at least 200 g / kg total compositions. - 17 022128 3. The composition according to claim 1 or 2, in which the herbicidally active ingredient is cyhalofop-butyl, phenoxaprop-ethyl, fluazifop-P-butyl, haloxyfop-methyl, haloxyfop-K-methyl, metamiphop, propacvisapop, quizalofop-R-ethyl kvizalofop -ethyl, p roksulam, imazethapyr, imazamox, imazosulfuron, and their derivatives. 4. The composition according to claim 1 or 2, wherein the herbicidally active ingredient is at least one of cyhalofop-butyl, penoxsulam, bensulfuron-methyl, azimsulfuron, imazosulfuron or fenoxprop-P-ethyl. 5. A stable herbicidal solid composition comprising an inherent adjuvant which includes: a) a herbicidally active ingredient selected from compounds having the formula where Ar is a phenyl group substituted by one to four substituents independently selected from halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₂ -C ₄ alkoxyalkyl, C ₂ -C ₆ alkylcarbonyl, C ₁ -C ₆ alkylthio groups, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ haloalkoxy, C ₂ -C ₄ haloalkoxyalkyl, C ₂ -C ₆ haloalkylcarbonyl, C ₁ -C ₆ haloalkylthio, —OCH ₂ CH ₂ -, —OCH ₂ CH ₂ CH ₂ -, —OCH ₂ O— or —OCH ₂ CH ₂ O—; K is H or P; X is C1 or vinyl; Υ is a C1, vinyl or methoxy group; their salts and esters, comprising in relation to the total weight of the composition from 1 to 200 g / kg; b) an integral adjuvant, comprising from 50 to 750 g / kg in relation to the total weight of the composition; c) solid carbohydrate constituting from 10 to 700 g / kg with respect to the total weight of the composition; b) a solid water-soluble polymer or oligomer constituting from 50 to 700 g / kg with respect to the total weight of the composition, provided that the solid carbohydrate and the solid water-soluble polymer or oligomer must together be at least 200 g / kg total compositions. 6. The composition according to claim 5, in which the herbicide is a compound of the following structure: where K is H or C 1 -C ₆ alkyl group. 7. The composition according to claim 6, in which K represents methyl. 8. The composition according to claim 5, which is presented in the form of granules or powder. 9. The composition according to claims 1, 2 or 5, in which the herbicidally active ingredient is from 2 to 75 g / kg. 10. A composition according to claims 1, 2 or 5, in which the integral adjuvant is an organic liquid immiscible with water. 11. A composition according to claims 1, 2 or 5, in which the essential adjuvant is selected from one or more organic water-immiscible organic liquids, which are petroleum distillates, hydrocarbons, mineral oil, kerosene, paraffin oils, mixed naphthalene and alkylnaphthalene fractions, aromatic solvents, alkyl substituted benzenes, xylene fractions, propyl benzene, vegetable oils, soybean oil, rapeseed oil, olive oil, castor oil, vegetable oil from sunflower seeds, coconut oil o, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil, vegetable oil esters, 2-ethyl hexyl stearate, n-butyl oleate, isopropyl myristate, dioleate, propylene glycol, methylated soybean oil and esters dibasic acids, dioctylsuccinate, dibutyl adipate, dioctyl phthalate, ditridecyl phthalate. 12. Composition according to claims 1, 2 or 5, in which the essential adjuvant is selected from one or more non-ionic surfactants, which are esters of fatty acid and polyhydric alcohol, polyethoxylated esters, polyethoxylated alcohols, alkyl polysaccharide derivatives or their mixtures, alkyl polyglycosides or their - 18,022,128 mixtures, amine ethoxylates, fatty acid ester ethoxylates, sorbitan silicone coatings, ethylene vinyl acetate terpolymers, ethoxylated alkylaryl phosphate esters or sucrose esters. 13. A composition according to claims 1, 2 or 5, in which the integral adjuvant is one or more of a paraffinic hydrocarbon oil, an aromatic hydrocarbon oil, vegetable oil or C ₁ -C ₆ ester of vegetable oil. 14. The composition according to claims 1, 2 or 5, in which the integral adjuvant is from 200 to 600 g / kg with respect to the total weight of the composition. 15. The composition according to 14, in which the integral adjuvant is in relation to the total weight of the composition from 300 to 600 g / kg. 16. The composition according to claims 1, 2 or 5, in which the solid carbohydrate is selected from one or more substances that represent monosaccharides, disaccharides, polysaccharides, glucose, fructose, sucrose, trehalose, lactose, maltose, dextrins, starches, modified starches, modified cellulose, alkylated cellulose, carboxyalkylated cellulose, natural gums, such as, for example, guar gums, xanthan gums, guar gums from seeds. 17. The composition according to claim 16, in which the solid carbohydrate is a monosaccharide or a disaccharide. 18. The composition according to claim 16, in which the solid carbohydrate is sucrose. 19. The composition according to claims 1, 2 or 5, in which the solid carbohydrate is in relation to the total weight of the composition from 10 to 500 g / kg, most preferably from 10 to 400 g / kg. 20. Composition according to claims 1, 2 or 5, in which the solid water-soluble polymer or oligomer is selected from one or more substances, which are lignosulfonates, alkylnaphthalene sulfonate and formaldehyde condensates, polyvinyl alcohols, polyacrylates, polyethylene oxides, polyvinylpyrrolidones or copolymers, their derivatives compound or mixture. 21. The composition according to claims 1, 2 or 5, in which the solid water-soluble polymer or oligomer is one or more of lignosulfonate, polyvinyl alcohol or alkylnaphthalene sulfonate condensate and formaldehyde. 22. The composition according to claims 1, 2 or 5, in which the solid water-soluble polymer or oligomer is in relation to the total weight of the composition from 100 to 600 g / kg, most preferably from 150 to 600 g / kg. 23. The composition according to claims 1, 2 or 5, further comprising one or more pesticidally active ingredients, plant growth regulators or antidotes. 24. The composition according to item 23, in which one or more of the herbicidally active ingredients selected from the group including clodinafop-propargil, cletodim, cycloxydim, diclofop-methyl, fenoxaprop-ethyl + isoxydiphene-ethyl, penoxadenum, sentoxydimy, tepraloxydim, tralkoksidim, 2,4-D, 2,4-MCPA esters and amines, 2,4-MCPA esters and amines, acetochlor, acifluorfen, alachlor, amidosulfuron, aminopyralide, aminotriazole, ammonium thiocyanate, aniliphos, benfuresate, bentazon, bentazon-sodium , bentiocarb, benzobicyclone, benzophenap, bifenox, bispyribac-sodium, rhombicus fluconamide Azone, Isobena propachlor, propanil, propisochlor, propisamide, prosulfuron, pyrubutikarb, pyrlonil, pyrazoogil, pyrazolinate, pyrazoxyfen, pyribenoxime, pyridate, pyridine, pyriminoxyl, pyriminoxyl, pyriminosaccharide, pyriminoxyl, pyriminosilane, pyriminosaccharide, pyriminosaccharide Sulcotrione, Sulfentrazone, Sulfosate, Tefuryltrione, Tenyl Chlor, Thiazopyr, Thiobencarb, Triafamone, Triclopyr, Triclopyr Esters and Amines, Trifluralin, Trinexapac-Ethyl and Tristosulfuron. 25. The composition of claim 23, wherein one or more of the antidotes are selected from the group consisting of benoxacor, benthiocarb, klokvintoset-mexyl, daimuron, dichlormid, ditsiklonon, dimepiperate, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, garpin protein , isoxadifen-ethyl, mefenpyr-diethyl, mefenate, MS 191, ΜΟΝ 4660, naphthoic anhydride (NA), oxabetrynyl, K29148, α-phenylsulfonylbenzoic acid amides and their derivatives. 26. The composition according to p. 25, in which one or more of the antidotes are cloquintoset-mexyl. 27. A method of controlling undesirable vegetation in an aqueous medium, which includes scattering, spraying or adding a herbicidally effective amount of a composition according to any one of claims 1, 2, 5 or 6 to the aqueous medium, both before and after the appearance of unwanted vegetation. 28. The method of claim 27, wherein the unwanted vegetation is controlled in the flooded rice. 29. A method of obtaining a stable herbicidal granular composition according to any one of claims 1, 5 or 6, which includes: a) mixing all solid water-soluble polymers or oligomers and solid carbohydrate ingredients in water to form an aqueous phase; b) mixing an essential adjuvant and oil-soluble or oil-dispersible active ingredients to form an oil phase; c) adding the oil phase obtained in stage b) to the aqueous phase obtained in stage a), with homogenization with a high shear rate to obtain a mixture; b) drying the mixture obtained in step c) to obtain a stable powder; e) agglomerating a stable powder obtained in stage b) by the method of granulation with a low shear pressure.